TWI413874B - Photoresist stripper composition - Google Patents

Abstract

Disclosed is a photoresist remover composition which enables to remove a photoresist without corroding Cu or Cu alloy wiring formed on a substrate during a wiring board manufacturing process for FPD. The composition contains 0.05-10% by weight of at least one heterocyclic compound selected from the group consisting of maltol, 2,6-dimethylgammapyrone, 4-hydroxy-6-methyl-2- pyrone, 4-hydroxycoumarin, 2,4-dihydroxyquinoline, 2-amino- 4,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine, 4,6-dimethyl-2- hydroxypyrimidine, uracil and 6-methyluracil, 5-45% by weight of a primary or secondary alkanol amine, and 50-94.95% by weight of a polar organic solvent and/or water.

Description

Photoresist stripper composition

The present invention relates to a resist release agent composition, and more particularly to a Cu or Cu alloy wiring substrate suitable for use in a flat panel display (hereinafter, also referred to as FPD) such as a liquid crystal display (hereinafter referred to as LCD). A photoresist stripper composition excellent in corrosion resistance and peelability.

The FPD is based on various display principles such as LCD, LED, EL, VFD, FED, SED, and PDP, and has an electrode structure to which fine wiring is applied, and a photoresist is used in the process. For example, in a liquid crystal display, a photoresist is applied to an insulating metal film such as Al, an Al alloy, Cu, or a Cu alloy formed on a substrate, or an insulating film such as a SiO ₂ film, and exposure and development are performed thereon. After the photoresist pattern is formed and the patterned photoresist is used as a mask, the conductive metal film or the insulating film is etched to form fine wiring, and then the unnecessary photoresist layer is removed by a stripping liquid.

Conventionally, as the photoresist release agent composition, a single solvent such as an organic base, an inorganic base, an organic acid, an inorganic acid or a polar solvent, or a mixed solution thereof is used. Moreover, in order to improve the peeling resistance, it is also known to use a mixture of an amine and water. For example, in the liquid crystal display, Al is widely used as a wiring material. Patent Document 1 discloses a photoresist release agent whose main component is an alkylamine or an alkanolamine, a polar organic solvent, and a ring-forming element which is a heterocyclic hydroxyl group-containing compound composed of nitrogen and carbon. To prevent or substantially inhibit the corrosion of Al.

However, in recent years, in response to the increase in the size of substrates, attempts have been made to use Cu, Cu alloys and the like having a lower resistivity than Al as wiring materials. Patent Document 2 discloses a heterocyclic compound having a five- or six-membered heterocyclic ring containing an atomic group consisting of -C(OH)=N- or -CONH-, and an anti-corrosive agent containing an alkanolamine to prevent formation. Corrosion of a metal film such as Cu on a semiconductor wafer.

In the photoresist used in the Al wiring forming step and the photoresist used in the Cu or Cu alloy wiring forming step, the photoresist itself is almost the same. However, in the stage of forming the fine wiring by etching the patterned photoresist as a mask, since the etching behavior of Al and Cu is completely different, it is necessary to form a wiring different from Al in the Cu or Cu alloy wiring forming step. The etching solution of the step. In general, an oxidizing agent-based etching liquid is used in the Cu or Cn alloy wiring forming step.

In order to be used as a mask, the patterned photoresist is deteriorated by the etching solution during wet etching. The degree of deterioration or deterioration varies depending on the etching liquid or etching conditions to be used, and the oxidant-based etching layer is used to form a photoresist layer which is deteriorated by the etching liquid for the Al wiring forming step, and the Cu or Cu alloy wiring forming step. The photoresist layer which is deteriorated by the liquid forms a metamorphic film which is very difficult to peel off. Therefore, it is difficult for the stripping liquid used in the Al wiring forming step to peel off the photoresist which is deteriorated by the etching liquid for the Cu or Cu alloy wiring forming step without causing damage to the wiring material.

In the above Patent Document 1, the state in which the Cu or Cn alloy wiring is formed is not considered, and it is difficult to peel off the deteriorated photoresist in the Cu or Cu alloy wiring forming step. Moreover, the corrosion inhibitor of Patent Document 2 has considered damage to the Cu corrosion-resistant or low-dielectric film, but since the use is limited to formation in the semiconductor The metal film on the bulk wafer, so the cause of the metamorphic film caused by the etching step is derived from the semiconductor etching method (for example, dry etching or ashing), so that the photoresist peeling force required for the FPD process is not obtained, and even It is a heterocyclic compound containing an atomic group consisting of -C(OH)=N-, and it is also incapable of exhibiting the Cu anticorrosive effect.

Patent Document 1: Japanese Patent Laid-Open Publication No. 2001-350276 Patent Document 2: Japanese Patent Laid-Open Publication No. 2002-97584

The present invention has been made in view of the above circumstances, and it is an object of the invention to provide a photoresist release agent composition which does not corrode Cu or Cu alloy wiring formed on a substrate and which can peel off the photoresist in the wiring substrate process of the FPD.

As a result of an effort to solve the above problems, the present inventors have found a composition containing a heterocyclic compound having a specific structure and containing an alkanolamine and a polar organic solvent and/or water, which is in a Cu or Cu alloy. In the wiring forming step, the wiring material is not corroded, and the photoresist layer which is deteriorated by the etching liquid for the Cu or Cu alloy wiring forming step can be peeled off, and the present invention has been completed.

That is, the present invention is a photoresist stripper composition which is a Cu or Cu alloy wiring forming step using FPD, which is characterized in that: Contains: free maltitol, 2,6-dimethyl γ-pyrone, 4-hydroxy-6-methyl-2-pyrone, 4-hydroxycoumalin, 2, 4-dihydroxyquinoline, 2-amino-4,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine, 4, 6-Dimethyl-2-hydroxypyrimidine, uracil, And at least one heterocyclic compound of the group consisting of 6-methyluracil, 0.05 to 10% by weight, 5 to 45% by weight of the primary or secondary alkanolamine, and 50 to 94.95% by weight of the polar organic solvent and/or water.

In one embodiment of the invention, the primary or secondary alkanolamine is selected from the group consisting of monoethanolamine, diethanolamine, n-propanolamine, monoisopropanolamine, monoethylethanolamine, aminoethoxyethanol, and monomethyl. At least one of the groups consisting of ethanolamine.

In another aspect of the present invention, the polar organic solvent is selected from at least one of the group consisting of diethylene glycol monobutyl ether, N-methylpyrrolidone, and dimethylacetamide.

The present invention is based on the above configuration,

1) In the wiring substrate process of the FPD, the photoresist layer which is deteriorated by the etching liquid for the Cu or Cu alloy wiring forming step has excellent photoresist peeling property.

2) Excellent corrosion resistance to wiring materials, that is, Cu or Cu alloy.

Hereinafter, the present invention will be described in detail.

The photoresist stripper composition of the present invention is a Cu or Cu alloy wiring forming step in FPD. The FPD is not particularly limited, and examples thereof include displays of the above various principles, and can be suitably applied to, for example, an LCD, a PDP, an EL, a VFD, and an SED.

Examples of the Cu alloy of the Cu or Cu alloy wiring include a low-oxygen Cu alloy and Cu-X (X is Sn, Zr, Be, Pb, Mo, Mn, and Fe, etc.) 2 A meta-alloy, and a three-element alloy such as Cu-Cr-Zr.

The heterocyclic compound used in the present invention is selected from the group consisting of free maltitol, 2,6-dimethyl γ-pyrone, 4-hydroxy-6-methyl-2-pyrone and 4-hydroxycoumarin. , 2,4-dihydroxyquinoline, 2-amino-4,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine At least one of the group consisting of 4,6-dimethyl-2-hydroxypyrimidine, uracil, and 6-methyluracil. More preferably, these are 2,4-dihydroxyquinoline, 2-amino-4,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, etc. from the viewpoint of stability over time and the like. And uracil may be used alone or in combination of two or more.

The amount of the heterocyclic compound added is 0.05% by weight to 10% by weight in the composition of the stripper. If the amount is less than this range, the anti-corrosion effect cannot be sufficiently exhibited. When the amount is more than this range, the amount of other components added is reduced, and the corrosion resistance is not particularly improved. It is preferably from 0.1% by weight to 5% by weight.

The primary or secondary alkanolamines used in the present invention are, for example, monoethanolamine (MEA), diethanolamine (DEA), n-propanolamine (NPA), monoisopropanolamine (MIPA), monoethylethanolamine (MEEA). , amino ethoxyethanol (EEA), and monomethylethanolamine (MMEA). The alkanolamine may be used alone or in combination of two or more. Among these, at least one selected from the group consisting of monoethanolamine, n-propanolamine, monoisopropanolamine, and monomethylethanolamine is preferred.

The amount of the alkanolamine added is from 5% by weight to 45% by weight of the release agent composition. If the amount is less than this range, the deteriorated photoresist layer cannot be sufficiently peeled off, and if it is added beyond this range, corrosion of the wiring material may occur. It is preferably from 10% by weight to 30% by weight.

The polar organic solvent used in the present invention may, for example, be diethylene glycol monobutyl ether (BDG), N-methylpyrrolidone (NMP), dimethylacetamide (DMAC), propylene glycol (PG), or dimethyl. Aachen (DMSO) and the like. These may be used alone or in combination of two or more. Among these, at least one selected from the group consisting of free diethylene glycol monobutyl ether, N-methylpyrrolidone, and dimethylacetamide is preferred.

In the present invention, only a polar organic solvent, water alone, or a combination of a polar organic solvent and water may be used.

The amount of the polar organic solvent and water added is, in each case, 50% by weight to 94.95% by weight in the composition of the stripper. If it is less than this range, the wiring material may be corroded or the deteriorated photoresist layer may be insufficiently peeled off. If the addition exceeds this range, the deteriorated photoresist layer may not be sufficiently peeled off. It is preferably 60% by weight to 90% by weight.

The photoresist stripper composition of the present invention can be prepared by mixing the amounts of the above components in a usual manner.

The photoresist peeling step of the FPD Cu or Cu alloy wiring forming step is for peeling off the photoresist after the oxidizing agent-based etching liquid for forming Cu or Cu alloy wiring, according to the wiring formation step of the LCD, and other types of FPD. The industry can also do it properly. The photoresist stripper composition of the present invention can be used by heating (for example, 30 ° C to 70 ° C). The time required for the peeling varies depending on the degree of deterioration of the photoresist, and is generally, for example, about 30 seconds to 10 minutes.

Further, the photoresist release agent composition of the present invention can be washed directly without washing with a solvent such as isopropyl alcohol after the release treatment.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to the examples. In addition, in the abbreviations in the table, the following abbreviations are as follows. Other abbreviations are as described above.

MDEA: N-methyl-N, N'-diethanolamine EDG: diethylene glycol monoethyl ether

Examples 1 to 27 and Comparative Examples 1 to 7

The components were separately mixed according to the blending of Table 1 to obtain a release agent composition. With respect to each of the obtained release agent compositions, the corrosion state of the wiring material at the time of the photoresist removal step was evaluated by the following method, and the corrosion state of the wiring material at the time of water washing in the case where the water washing was directly performed after the peeling treatment was assumed. Table 2 shows the results of the evaluation.

Evaluation 1. Cu corrosion during photoresist stripping Evaluation of the corrosion condition of the wiring material in the photoresist stripping step, in the stripper When the composition contains water, the Cu film substrate is immersed in a release agent at 40 ° C for a predetermined period of time, and when the release agent composition contains no water, the Cu film substrate is immersed at 70 ° C for a predetermined period of time. The etching rate (Å/min) of Cu was determined from the amount of decrease in the film thickness of the Cu film, and was evaluated by the following criteria.

2. Cu corrosion during water washing The evaluation of the corrosion condition of the wiring material in the water washing step after the photoresist stripping is performed by immersing the Cu film substrate with water at a predetermined time to dilute the stripping agent composition to a normal temperature test liquid of 10 times, and according to the film thickness of the Cu film. The etching rate (Å/min) of Cu was determined by the amount of reduction, and was evaluated by the following criteria. Further, the reason why the release agent was diluted 10 times with water was that the peeling agent: water ratio was 1:9, and the corrosion rate of the wiring material was the maximum.

The evaluation criteria for the etch rate measurement are as follows. ○ The above is acceptable. The unit is Å/min.

3. Photoresist stripping The peeling state of the photoresist layer which deteriorated with the oxidizing agent etching liquid was evaluated by the following method. In addition, the evaluation of the corrosion condition of the wiring material was not performed for the poorly peelable one.

(1) Method for producing metamorphic film for evaluation A positive photoresist (NPR3510S1 10 mPa.s manufactured by Nagase ChemteX Corporation) was coated with a 15000 Å wafer by a spin coater and prebaked at 100 ° C for 2 minutes. This is passed through a reticle and exposed and developed to form a photoresist pattern. The ruthenium wafer in which the photoresist pattern was formed was immersed in an oxidizing agent-based etching solution at 40 ° C for 1 minute to prepare a metamorphic film for evaluation. After washing with water and drying with nitrogen, this was subdivided into sample sheets for evaluation.

(2) Peeling evaluation method In the peeling treatment, when the release agent composition contains water, the sample piece is immersed in a release agent composition at 40 ° C, and when water is not contained, the sample piece is immersed in a release agent composition at 70 ° C, and gently stirred for 1 minute. Process it. After the completion of the treatment, the sample piece was taken out, immediately washed with water and dried with nitrogen, and the residual state of the photoresist peeling was observed under an optical microscope.

The evaluation criteria for peelability are as follows. ○ The above is acceptable.

◎: no photoresist residue ○: although the photoresist pattern cannot be seen, there is a trace of photoresist residue Δ: the photoresist pattern can be seen faintly: the photoresist pattern can be clearly seen

As is clear from Table 2, Examples 1 to 25 were excellent in corrosion resistance of Cu, and the peeling property of the photoresist layer which was deteriorated by the oxidizing agent-based etching liquid was also good. On the other hand, in Comparative Examples 1 and 2 which did not contain the heterocyclic compound used in the present invention, Cu corrosion was observed. Comparative Example 3 in which the content of the alkanolamine is less than the range of the present invention The peeling property was not good, and Cu corrosion was observed in Comparative Example 4 in which the range was exceeded. In Comparative Example 5 containing a heterocyclic compound having an atomic group composed of -C(OH)=N- or -CONH- which is not a heterocyclic compound used in the present invention, there is no Cu anticorrosive effect and Cu corrosion can be observed. Further, in Comparative Example 6 using a tertiary alkanolamine, the peeling property was poor. Further, Comparative Example 7 in which the composition of the solvent was not added without adding an amine was also inferior in peelability. In the case of Example 26, although the viscosity is high, the load of the liquid feeding pump of the peeling device may increase in practical use, but the corrosion resistance of Cu is excellent, and the peeling property of the photoresist layer is also good. In Example 27, although there was a solvent odor, Cu corrosion resistance was also good, and the peeling property of the photoresist layer was also excellent.

Claims (3)

A photoresist stripper composition for forming a Cu or Cu alloy wiring for a flat panel display, comprising: selecting at least one of a group consisting of free uracil and 6-methyluracil The cyclic compound is 0.05 to 10% by weight, the primary or secondary alkanolamine is 5 to 45% by weight, and the polar organic solvent and/or water is 50 to 94.95% by weight. The photoresist stripper composition of claim 1, wherein the primary or secondary alkanolamine is selected from the group consisting of monoethanolamine, diethanolamine, n-propanolamine, monoisopropanolamine, monoethylethanolamine, and amine. At least one of the group consisting of ethoxyethoxyethanol and monomethylethanolamine. The photoresist stripper composition according to claim 1 or 2, wherein the polar organic solvent is selected from the group consisting of free diethylene glycol monobutyl ether, N-methylpyrrolidone, and dimethylacetamide. At least one of the groups.